Mineral oil solutions



Patented May 28, 1940 UNITED STATES PATENT OFFICE MINERAL 01L SOLUTIONSEric C. Kunz, Montclalr, and Alphonse T. Flore,

Passaic, N. J., assignors to Givaudan-Dela- -wanna, Inc., New York, N.Y., a corporation of New York No Drawing. Application March 26, 1938,Serial No. 198,228

7 Claims.

' for liquid sprays,-particularly. for insecticides,

paint sprays, perfume sprays, pharmaceutical products, etc.; but certainorganic substances, which would otherwise be highly effective as theactive ingredients of such sprays, have heretofore not been used becausethey are insoluble or only slightly soluble in such mineral oildistillates. Among such organic substances may be mentioned rotenone,oleoresins containing rotenone, vanillin, coumarin, dibenzylideneacetone, rosin, olibanum oleoresin, etc.

We have now discovered that alkyl phenols of the general formula:

. R, and mixtures of such phenols have an unexpected solvent effect formaintaining in mineral oil distillates the above-mentioned organicsubstances which are soluble in alkyl phenols but are otherwiseinsoluble or only slightly soluble in the mineral oil itself. R and ITin the above formula are alkyl groups ,while R2 may be hydrogen or analkyl group so that the total number of carbon atoms in the alkyl groupsis not less than 3 and does not exceed 16.

We have also'found that these alkyl phenols increase the compatibilityof other phenolic and As specific examples of alkyl phenols according tothe above formula may be mentioned:

Mono and di isopropyl phenols and cresols, such as thymol and carvacrol,and mono isopropyl xylenols. 5 Butyl and isobutyl cresolsand xylenols.Amyl and isoamyl cresols and xylenols. Dibutyl and di isobutyl phenolsand cresols. Dlamyl and di isoamyl phenols and cresols.

Dioctyl phenol. Natural products containing such phenols as forinstance, oil thyme, origanum, etc.

It is to be noted, however, that the various alkyl phenols differ intheir eificiency for main- 1-5 taining rotenone and other substances insolution. For instance, 45% of mono or di-iso propyl cresol willmaintain .05% rotenone in a 40 Saybolt viscosity mineral oil whereas 1%of cresols or xylenols are necessary to obtain the same 20.-

effect. For maintaining in mineral oil solution such products asrotenone and the other active principles found in Derris, cube, etc. thegreatest efliciericy is exhibited by alkyl phenols in which the totalnumber of carbon atoms in the alkyl 25 groups varied between 3 and 8.Likewise a change in the viscosity of the mineral oil as well as achange in the rotenone concentration will necessarily affect theconcentration of the solvent required to maintain a given concentration3 of rotenone in solution.

For instance, of 1% 'ofiso propyl xylenol will maintain .05% rotenone ina 40 Saybolt vis-' cosity mineral oil while only 3% of iso propylxylenol is necessary to maintain .5%' rotenone solution in the samemineral oil; or expressed otherwise, 10 parts of alkyl phenols and .1part of rotenone or rotenone oleoresins will maintain the rotenone inmineral oil solution in all'concem trations above .05% while a ratio ofonly 6 parts 40 of alkyl phenol to 1 part of rotenone is required formineral oil solutions containing more than of rotenone.

In cases where the phenolic derivative is solid and has a markedtendency to crystallize from mineral oil solutions, this can readily beovercome by mixing therewith other phenolic or nonphenolic substances soas to obtain a liquid or low melting solution which does not crystallizefrom mineral oil.

Para tertiary arnyl phenol or high melting isomers of thymol orcarvacrol'when used alone tend to crystallize from mineral oil. However,by mixing these with such phenols as thymol, carvacrol or other liquidphenols a satisfactory solution results. In the above proportions thealkyl phenol or alkyl phenol mixture can be replaced to the extent of5-40% by materials listed above such as pine oil, oleic acid, camphoroil, dimethyl aniline, etc.

The above facts are of utmost importance in the production of rotenonesprays for use as insecticides. For the manufacture of a satisfactoryoil spray for instance, according to the time of the year, the insectwhich is to be killed, the nature of the plant to be protected, it isabsolutelynecessary that the volatility of the solvent and theconcentration of the rotenone be properly adjusted, and this can best beaccomplished by using a mixture of mineral oils and selecting the properalkyl phenol or mixtures thereof. All these factors can be adjusted tothe utmost nicety through the use of the present invention, it beingpossible to regulate the volatility of the various ingredients within awide range. Of course, it goes without saying that other inert or activeproducts may be mixed with rotenone, that other oils or diluents may bemixed with the mineral oil, and that a. suitable emulsifier may be addedto the mineral oil solution so as to make water sprays from thecompounds.

The terms mineral oil and mineral oil distillate as used herein aremeant to include those petroleum distillates or their hydrogenationproducts which are suitable for use in plant or animal sprays of aninsecticidal nature, including products of similar nature obtained inthe distillation of products of coal liquefaction or coal hydrogenation.All these products are distillates in which most of the constituentsharmful to plants and animals such as nitrogen compounds, sulfurcompounds, unsaturated hydrocarbons, pitches, tars and residues, havebeen removed. The distillates best suited to this purpose are thekerosene and mineral oil fractions or mixtures of both and also theirhydrogenated products which have a high unsulfonated residue indicatinga high percentageof saturated hydrocarbons. I'he suitable mineral oilfraction will have a Saybolt viscosity of 40-120.

These distillates all have a slight solubility for rotenone. At roomtemperature a deodorized kerosene of a specific gravity at 25 of .776will dissolve .01% rotenone. A mineral oil of 60 Saybolt viscosity willdissolve .023% rotenone. We have made the unforeseen discovery thatphenolic compounds, when added in small quantities to kerosene ormineral oil or to mixtures of both, appreciably increase the solventpower for rotenone. Using a mixture consisting of 50% each of keroseneand a white mineral oil Saybolt viscosity 60, the solubility of rotenonewill be influenced as follows by the addition of phenolic products.

Kerosene Phenolic Rotenone g gg g 1}, solubility Parts Parts Percent 99.5 5 05 99. 0 l. 0 1 98. 0 2. 0 3 97. 0 3. 0 5

lution. Plant sprays containing such large quantities of solvents willbe harmful to the plants, as a rule causing undesirable secondaryeffects like burning of leaves.

With the phenolic compounds used accordin to the present invention, aslittle as will be required for a stable plant spray containing .05%rotenone and therein lies the decided advantage over all other knownsolvents. The phenolic compounds have the further very desirable qualityof low volatility insuring their remaining in the mineral oil orkerosene after spraying, thereby keeping the rotenone in solution, or inother words in molecular dispersion which is the state of highestinsecticidal activity. The volatility of the phenolic compounds usefulwithin the scope of thisinvention on the other hand is of an ordergreater than that of mineral oil, which quality will avoid the formationof harmful concentrations after spraying.

In preparing insecticidal solutions containing mineral oil or keroseneor both, together with rotenone and the other toxic insecticidalsubstances contained in the oleoresin of Derris, cube, timbo, etc., weprefer to first dissolve the rotenone or rotenone containing oleoresinin the alkyl phenol or mixture of these phenols, making a solution of 1part by weight of rotenone and 5-10 parts by weight of the phenol orphenol mixture. This concentrated solution can then be diluted withmineral oil or kerosene or both to yield finished insecticidal sprayscontaining from .05 to .5% rotenone or oleoresins containing rotenone.If necessary for special purposes solutions of concentrations which arehigher than ..5% rotenone can be obtained by addition of less mineraloil. Such solutions are useful for emulsification with water or otheremulsified sprays.

Our rotenone solutions in mineral oil are mixable with pyrethrumextracts and organic thiocyanates and iso thiocyanates and are thereforevery useful to strengthen these other insecticidal solutions.

In connection with the foregoing methods and compositions, we mightmention that it is easier to dissolve rotenone than to dissolve theoleoresin containing rotenone as obtained in the extraction of Derris,cube, timbo root, etc., with solvents. The composition of the oleoresindepends to some extent on the organic solvent used for the extraction.By using our invention it is possible to employ Derris, cube, etc.,oleoresin manufactured with any of thecommonly used solvents as thephenolic compounds have the very great advantage of selectivelydissolving only the insecticidally active ingredients of the oleoresin.The undesirable material can easily be eliminated by filtration of thesolution of the oleoresin in the phenolic compounds. This represents avery simple way of refining the oleo resin which is of great practicalvalue.

It will be evident to those skilled in the art that various changes maybe made in the foregoing compositions and methods of manufacture withoutdeparting from the scope and spirit of the invention as defined in theappended claims.

The invention claimed is:

1. A liquid insecticide comprising a solution of the following materialsin substantially the following proportions by weight: mineral oildistillate 96.5%, iso propyl cresols 2.25%, pine oil 0.75%, and rotenoneor an oleoresin containing rotenone 0.5%.

2. Insecticidal compositions containing minera1 oil distillate, an alkylsubstituted cresol selected from the class consisting of butyl andisobutyl cresols, and a third substance selected from the groupconsisting of rotenone, oleoresins containing rotenone, and theinsecticidally-active principles of Derris, cube and timbo, said thirdsubstance being present in said composition in an amount greater thanits normal solubility in said mineral oil alone.

3. An insecticidal composition containing mineral oil distillate, analkyl phenol selected from the group consisting of thymol and itsisomers, and a third substance selected from the group consisting ofrotenone, oleoresins containing rotenone, and the insecticidally-activeprinciples of Derris, cube and timbo, said third substance being presentin said composition in an amount greater than its normal'solubility insaid mineral oil alone. 1

4. An insecticidal composition containing mineral oil distillate, apoly-alkyl phenol of the general formula wherein R and R1 arealkylgroups and R2 is H or alkyl, the total number of carbon atoms in thealkyl groups being not less than 3 and not more than 16, each alkylgroup containing not more than 8 carbon atoms therein, and a thirdsubstance selected from the group consisting of the alkyl groups beingnot less than 3 and not more than 16, each alkyl group containing notmore than 8 carbon'atems therein, and at least 0.05% of a thirdsubstance selected from the group consisting of rotenone, oleoresinscontaining rotenone, and insecticidally-active principles of Derris,cube and timbo.

6. An insecticidal composition containing mineral oil distillate, apoly-alkyl phenol of the general formula wherein R and R1 are alkylgroups and R2 is H or alkyl, the total number of carbon atoms in thealkyl groups being not lessthan 3 and not more than 16, each alkyl groupcontaining not more than 8 carbon atoms therein, and arotenonecontaining substance, said rotenone-containing substance beingpresentin said composition in an amount greater than its normalsolubility in said mineral oil alone.

7. An insecticidal composition containing mineral oil distillate, apoly-alkyl phenol of the general formula Rz wherein R and R1 are alkylgroups and R: is H or alkyl, the total number of carbon atoms in thealkyl groups being not less than 3 and not more than 16, each alkylgroup containing not more than 8 carbon atoms therein, and 0.05%0.5% ofa rotenone containing substance.

ERIC 0. KUNZ. ALPHONSE T. FIORE.

